Ion conductive solid and all-solid-state battery

Abstract

The present invention provides an ion conductive solid which contains an oxide that is represented by formula Li6+a-c-2dX1-a-b-c-dM1aM2bM3cM4dB3O9. (In the formula, X represents at least one metal element that is selected from the group consisting of Lu, Ho, Er and Tm; M1 represents at least one metal element that is selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba; M2 represents at least one metal element that is selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc; M3 represents at least one metal element that is selected from the group consisting of Zr, Ce, Hf, Sn and Ti; M4 represents at least one metal element that is selected from the group consisting of Nb and Ta; a, b, c and d are specific real numbers; and the cases where X and M2 represent the same metal element are excluded.)

Description

Ion-conducting solid and all-solid-state batteries

[0001] The present disclosure relates to ion-conducting solids and all-solid-state batteries.

[0002] Lightweight, high-capacity lithium-ion secondary batteries have traditionally been installed in mobile devices such as smartphones and laptops, as well as in transportation equipment such as electric vehicles and hybrid electric vehicles. However, conventional lithium-ion secondary batteries use a liquid electrolyte containing a flammable solvent, raising concerns about the risk of the flammable solvent leaking and fires in the event of a short circuit. Therefore, in recent years, to ensure safety, secondary batteries that use an ionically conductive solid electrolyte, rather than a liquid electrolyte, have attracted attention. These secondary batteries are known as all-solid-state batteries.

[0003] Widely known solid electrolytes used in all-solid-state batteries include oxide-based solid electrolytes and sulfide-based solid electrolytes. Of these, oxide-based solid electrolytes are safer than sulfide-based solid electrolytes because they do not react with moisture in the air to produce hydrogen sulfide.

[0004] Incidentally, an all-solid-state battery has a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, an electrolyte containing an ion-conductive solid disposed between the positive electrode and the negative electrode, and, if necessary, a current collector (the positive electrode active material and the negative electrode active material are collectively referred to as "electrode active material"). When an all-solid-state battery is fabricated using an oxide-based solid electrolyte, a heat treatment is performed to reduce the contact resistance between particles of the oxide-based material contained in the solid electrolyte. However, conventional oxide-based solid electrolytes require a high temperature of 900°C or higher for the heat treatment, which may result in a reaction between the solid electrolyte and the electrode active material to form a high-resistance phase. This high-resistance phase may lead to a decrease in the ionic conductivity of the ion-conductive solid, and ultimately to a decrease in the output of the all-solid-state battery. Oxide-based solid electrolytes that can be fabricated by heat treatment at temperatures below 900°C include Li ２＋ｘ C １－ｘ B ｘ O ３ (Non-Patent Document 1). ２＋ｘ C １－ｘ B ｘ O３ However, it has been disclosed that the properties can be improved by including specific elements in specific ratios (Patent Document 1).

[0005] Solid State Ionic 288 (2016) 248-252 Acta Crystallographica Section A 32 (1976) 751

[0006] Patent No. 6948676

[0007] The present disclosure provides an ion-conductive solid that can be produced by heat treatment at a low temperature and has high ion conductivity, and an all-solid-state battery having the same.

[0008] The ionically conductive solids of the present disclosure have the general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ (wherein X is at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti, and M4 is at least one metal element selected from the group consisting of Nb and Ta, a is a real number that satisfies 0.000≦a≦0.800, b is 0.000≦b≦0.900, c is 0.000≦c≦0.800, d is 0.000≦d≦0.800, and a, b, c, and d are real numbers that satisfy 0.000≦a+b+c+d<1.000, except when X and M2 are the same metal element.)

[0009] The all-solid-state battery according to the present disclosure is an all-solid-state battery having at least a positive electrode, a negative electrode, and an electrolyte, wherein at least one selected from the group consisting of the positive electrode, the negative electrode, and the electrolyte contains the ion-conducting solid according to the present disclosure.

[0010] According to one aspect of the present disclosure, it is possible to obtain an ion-conductive solid that can be produced by a heat treatment at a low temperature and has high ion conductivity, and an all-solid-state battery including the ion-conductive solid.

[0011] In this disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, in this disclosure, "solid" refers to a substance that has a certain shape and volume among the three states of matter, and a powder state is included in "solid."

[0012] The ionically conductive solids of the present disclosure have the general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９In the formula, X is at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti, and M4 is at least one metal element selected from the group consisting of Nb and Ta. a is a real number that satisfies 0.000≦a≦0.800, b is 0.000≦b≦0.900, c is 0.000≦c≦0.800, d is 0.000≦d≦0.800, and a, b, c, and d are real numbers that satisfy 0.000≦a+b+c+d<1.000, except when X and M2 are the same metal element. The phrase "excluding the case where X and M2 are the same metal element" means that when X is Lu, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, In, Fe, and Sc, when X is Ho, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Lu, In, Fe, and Sc, when X is Er, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Lu, In, Fe, and Sc, When X is Tm, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Lu, In, Fe, and Sc.

[0013] The present inventors speculate that the reason why the ionic conductivity is improved in the ion-conductive solid containing the oxide represented by the above general formula is as follows. ６ YB ３ O ９By substituting Y in the formula (I) with at least one selected from the group consisting of Lu, Ho, Er, and Tm, which are metal elements having a smaller ionic radius than Y, the lattice constant and the lattice volume are reduced. ＋ On the other hand, in Patent Document 1, a part of the trivalent metal element Y is substituted with a tetravalent or pentavalent metal element, that is, by substituting elements with different valences, the charge balance is adjusted and the ionic conductivity is improved. In this way, by using a metal element with an appropriate ionic radius as the metal element X instead of Y, the lattice constant and lattice volume are reduced. As a result, Li ＋ The ionic conductivity is further improved because the atoms move more easily. Furthermore, it is also a preferred embodiment to use element substitutions with different valences in combination.

[0014] The ionic radius of X is preferably 0.900 to 1.017 Å, more preferably 0.920 to 1.015 Å, even more preferably 0.940 to 1.015 Å, and particularly preferably 0.975 to 1.015 Å. By being in the above range, the lattice constant and lattice volume become small. As a result, Li ＋ The ionic conductivity is improved because the ions move more easily. If the ionic radius is less than 0.900 Å, the desired monoclinic structure cannot be obtained, and the solid will not be an ion-conductive solid. The value of the ionic radius can be the value described in Non-Patent Document 2. For example, ３＋ The ionic radius of Lu is 1.019 Å. ３＋ The ionic radius of Ho is 0.977 Å. ３＋ The ionic radius of Er is 1.015 Å. ３＋ The ionic radius of is 1.004 Å, and Tm ３＋ The ionic radius of is 0.994 Å.

[0015] The ionically conducting solids of the present disclosure preferably have a monoclinic crystal structure.

[0016] The ion conductive solid of the present disclosure preferably has a volume average particle size of 0.1 μm or more and 28.0 μm or less, more preferably 0.2 μm or more and 26.0 μm or less, even more preferably 0.3 μm or more and 20.0 μm or less, even more preferably 0.3 μm or more and 15.0 μm or less, and even more preferably 0.5 μm or more and 10.0 μm or less. By being in the above range, the grain boundary resistance within the ion conductive solid is reduced, and the ionic conductivity is further improved. The volume average particle size of the ion conductive solid can be controlled by pulverization or classification.

[0017] In the above general formula, a is a real number that satisfies 0.000≦a≦0.800, preferably 0.000≦a≦0.600, more preferably 0.000≦a≦0.400, even more preferably 0.000≦a≦0.100, particularly preferably 0.000≦a≦0.050, and extremely preferably 0.000≦a≦0.030.

[0018] In the above general formula, b is a real number that satisfies 0.000≦b≦0.900, preferably 0.000≦b≦0.600, more preferably 0.000≦b≦0.500, even more preferably 0.000≦b≦0.400, still more preferably 0.000≦b≦0.100, particularly preferably 0.000≦b≦0.050, and extremely preferably 0.000≦b≦0.030.

[0019] In the above general formula, c is a real number satisfying 0.000≦c≦0.800. c is 0.000≦c≦0.800, preferably 0.000≦c≦0.600, more preferably 0.000≦c≦0.400, even more preferably 0.000≦c≦0.150, still more preferably 0.000≦c≦0.100, particularly preferably 0.000≦c≦0.050, and extremely preferably 0.000≦c≦0.030. Furthermore, C may be preferably 0.050≦c≦0.200, more preferably 0.080≦c≦0.150.

[0020] In the above general formula, d is a real number satisfying 0.000≦d≦0.800, preferably 0.000≦d≦0.600, more preferably 0.000≦d≦0.400, even more preferably 0.000≦d≦0.100, particularly preferably 0.000≦d≦0.050, and extremely preferably 0.010≦d≦0.030.

[0021] In the above formula, a+b+c+d is a real number satisfying 0.000≦a+b+c+d<1.000. a+b+c+d is 0.000≦a+b+c+d<1.000, preferably 0.000≦a+b+c+d<0.900, more preferably 0.000≦a+b+c+d<0.800, even more preferably 0.000≦a+b+c+d<0.700, still more preferably 0.000≦a+b+c+d<0.600, particularly preferably 0.010≦a+b+c+d<0.500, particularly preferably 0.050≦a+b+c+d<0.300, and extremely preferably 0.080≦a+b+c+d<0.250.

[0022] X １－ａ－ｂ－ｃ－ｄ In the formula, 1-a-b-c-d is preferably 0.300≦1-a-b-c-d, more preferably 0.500≦1-a-b-c-d, even more preferably 0.700≦1-a-b-c-d, and even more preferably 0.750≦1-a-b-c-d. The upper limit is not particularly limited, but is preferably less than 1.000, 0.950 or less, or 0.900 or less. For example, preferred ranges include 0.300≦1-a-b-c-d<1.000, 0.500≦1-a-b-c-d≦0.950, and 0.700≦1-a-b-c-d≦0.900.

[0023] The ion-conducting solid of the present disclosure may have the following embodiments, for example, but is not limited to these. (1) a may satisfy 0.010≦a≦0.100, b may satisfy 0.000≦b≦0.200, c may satisfy 0.000≦c≦0.200, d may satisfy 0.010≦d≦0.100, and a, b, c, and d may satisfy 0.010≦a+b+c+d<0.300. (2) a may satisfy 0.010≦a≦0.030, b may satisfy 0.030≦b≦0.100, c may satisfy 0.010≦c≦0.030, d may satisfy 0.010≦d≦0.030, and a, b, c, and d may satisfy 0.050≦a+b+c+d<0.160. (3) a satisfies 0.000≦a≦0.010, b satisfies 0.000≦b≦0.100, c satisfies 0.050≦c≦0.150, d satisfies 0.000≦d≦0.030, and a, b, c, and d satisfies 0.050≦a+b+c+d<0.250. M1, M2, M3, and M4 in the above general formula may or may not be included in the formula. That is, at least one of a, b, c, and d may be 0.

[0024] In the above general formula, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba. M1 is at least one selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba, preferably at least one selected from the group consisting of Mg, Zn, Ca, Sr, and Ba, and more preferably at least one selected from the group consisting of Mg, Ca, and Sr.

[0025] In the above general formula, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc. M2 is at least one selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc, preferably at least one selected from the group consisting of La, Eu, Gd, Tb, Dy, Lu, In, and Fe, more preferably at least one selected from the group consisting of Gd, Dy, Lu, In, and Fe. M2 may also be at least one selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, In, Fe, and Sc.

[0026] In the above general formula, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti. M3 is at least one selected from the group consisting of Zr, Ce, Hf, Sn, and Ti, preferably at least one selected from the group consisting of Zr, Ce, Hf, and Sn, and more preferably at least one selected from the group consisting of Zr, Ce, and Hf.

[0027] In the above general formula, M4 is at least one metal element selected from the group consisting of Nb and Ta. M4 is at least one element selected from the group consisting of Nb and Ta, and is preferably Nb.

[0028] Furthermore, when a part of the trivalent metal element X is substituted with specific elements M1, M2, M3, and M4 in a specific ratio range, the charge balance is adjusted by the substitution of elements with different valences. ＋ becomes missing. ＋ In order to fill the gap, the surrounding Li ＋ This increases the ionic conductivity.

[0029] Next, a method for producing an ion-conductive solid according to the present disclosure will be described. The method for producing an ion-conductive solid according to the present disclosure can be implemented in the following manner, but is not limited thereto. ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａM2 ｂ M3 ｃ M4 ｄ B ３ O ９ The present invention relates to a method for producing an ion-conductive solid containing an oxide represented by the general formula (I), which may include a primary firing step of heat-treating raw materials mixed so as to obtain an oxide represented by the general formula at a temperature below the melting point of the oxide, wherein X is at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti, and M4 is at least one metal element selected from the group consisting of Nb and Ta. a is a real number that satisfies 0.000≦a≦0.800, b is 0.000≦b≦0.900, c is 0.000≦c≦0.800, d is 0.000≦d≦0.800, and a, b, c, and d are real numbers that satisfy 0.000≦a+b+c+d<1.000, except when X and M2 are the same metal element.

[0030] The method for producing an ion-conductive solid according to the present disclosure may include a primary firing step in which raw materials are weighed and mixed so as to obtain an oxide represented by the above general formula, and the raw materials are heat-treated at a temperature below the melting point of the oxide to produce an ion-conductive solid containing the oxide. The ion-conductive solid can be obtained by the primary firing step. Furthermore, the production method may optionally include a secondary firing step in which the obtained ion-conductive solid containing the oxide is heat-treated at a temperature below the melting point of the oxide to produce a sintered body of the ion-conductive solid containing the oxide. Below, the method for producing an ion-conductive solid according to the present disclosure, which includes the primary firing step and the secondary firing step, will be described in detail, but the present disclosure is not limited to the production method described below.

[0031] First firing step In the first firing step, the general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ (wherein X is at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm; M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba; M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc; M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti; M4 is at least one metal element selected from the group consisting of Nb and Ta; a is a real number that satisfies 0.000≦a≦0.800, b is 0.000≦b≦0.900, c is 0.000≦c≦0.800, d is 0.000≦d≦0.800, and a, b, c, and d are real numbers that satisfy 0.000≦a+b+c+d<1.000. However, this does not apply when X and M2 are the same metal element.) ２ CO ３ , H ３ BO ３ , Ho ２ O ３ , ZrO ２ , CeO ２ , HfO ２ The raw materials are weighed in stoichiometric amounts and mixed.

[0032] The mixing equipment is not particularly limited, but a pulverizing mixer such as a planetary ball mill can be used. The material and capacity of the container used during mixing, as well as the material and diameter of the balls, are not particularly limited and can be selected appropriately depending on the type and amount of raw materials used. As an example, a 45 mL container made of zirconia and 5 mm diameter zirconia balls can be used. The mixing conditions are not particularly limited, but can be, for example, a rotation speed of 50 rpm to 2000 rpm and a time of 10 to 60 minutes. After obtaining a mixed powder of the raw materials through this mixing process, the resulting mixed powder is pressure-molded into pellets. Known pressure-molding methods, such as cold uniaxial molding and cold isostatic pressing, can be used as the pressure-molding method in the primary firing step. The pressure-molding conditions in the primary firing step are not particularly limited, but can be, for example, a pressure of 100 MPa to 200 MPa. The resulting pellets are then fired using a firing device such as an air firing device. The temperature at which the solid-phase synthesis is carried out by primary baking is determined by the general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ There are no particular limitations on the temperature as long as it is below the melting point of the ion-conductive solid represented by the formula: The temperature during primary firing can be, for example, below 700°C, 680°C or less, 670°C or less, 660°C or less, or 650°C or less, and can be, for example, 500°C or more. The numerical ranges can be arbitrarily combined. If the temperature is within the above range, solid-phase synthesis can be carried out sufficiently. The time for the primary firing step is not particularly limited, but can be, for example, about 700 to 750 minutes. The primary firing step produces a compound of the general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９It is possible to prepare an ion-conductive solid containing an oxide represented by the formula: The ion-conductive solid containing the oxide can also be pulverized using a mortar and pestle or a planetary mill to obtain a powder of the ion-conductive solid containing the oxide.

[0033] Secondary Firing Step In the secondary firing step, at least one selected from the group consisting of the ion-conductive solid containing an oxide obtained in the primary firing step and a powder of the ion-conductive solid containing an oxide is pressure-molded as necessary and fired to obtain a sintered body of the ion-conductive solid containing an oxide. The pressure molding and secondary firing may be performed simultaneously using spark plasma sintering (hereinafter also simply referred to as "SPS") or a hot press, or a pellet may be produced by cold uniaxial molding and then secondary fired in an air atmosphere, an oxidizing atmosphere, or a reducing atmosphere. Under the above conditions, an ion-conductive solid with high ionic conductivity can be obtained without melting due to heat treatment. The pressure molding conditions in the secondary firing step are not particularly limited, but can be, for example, a pressure of 10 MPa to 100 MPa. The secondary firing temperature is set to a value of 100 MPa to 100 MPa, based on the general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ The temperature during secondary firing is preferably less than the melting point of the ion-conductive solid represented by the formula (1). The temperature during secondary firing is preferably less than 700°C, more preferably 680°C or less, even more preferably 670°C or less, and particularly preferably 660°C or less. The lower limit of the temperature is not particularly limited, and the lower the better, but it is, for example, 500°C or higher. The numerical ranges can be arbitrarily combined, and can be, for example, a range of 500°C or higher and lower than 700°C. Within the above range, melting or decomposition of the ion-conductive solid containing the oxide of the present disclosure can be suppressed during the secondary firing step, and a sufficiently sintered sintered body of the ion-conductive solid containing the oxide of the present disclosure can be obtained. The time for the secondary firing step can be appropriately changed depending on the temperature, pressure, etc. of the secondary firing, but is preferably 24 hours or less, and may be 14 hours or less. The time for the secondary firing step may be, for example, 5 minutes or more, 1 hour or more, or 6 hours or more.

[0034] The method for cooling the sintered body of the ion-conductive solid containing the oxide of the present disclosure obtained by the secondary firing step is not particularly limited, and the cooling may be performed naturally (cooling in a furnace), rapidly, or more gradually than naturally, or may be maintained at a certain temperature during cooling.

[0035] Next, the all-solid-state battery of the present disclosure will be described. An all-solid-state battery generally includes a positive electrode, a negative electrode, an electrolyte containing an ion-conductive solid disposed between the positive electrode and the negative electrode, and a current collector as needed.

[0036] The all-solid-state battery of the present disclosure is an all-solid-state battery having at least a positive electrode, a negative electrode, and an electrolyte, wherein at least one selected from the group consisting of the positive electrode, the negative electrode, and the electrolyte contains the ion-conducting solid of the present disclosure.

[0037] The all-solid-state battery of the present disclosure may be a bulk battery or a thin-film battery. The specific shape of the all-solid-state battery of the present disclosure is not particularly limited, but examples thereof include a coin type, a button type, a sheet type, and a laminate type.

[0038] The all-solid-state battery of the present disclosure has an electrolyte. In addition, in the all-solid-state battery of the present disclosure, it is preferable that at least the electrolyte contains the ion-conductive solid of the present disclosure. The solid electrolyte in the all-solid-state battery of the present disclosure may be made of the ion-conductive solid of the present disclosure, or may contain other ion-conductive solids, or may contain an ionic liquid or a gel polymer. The other ion-conductive solid is not particularly limited, and may be an ion-conductive solid typically used in all-solid-state batteries, such as LiI, Li ３ P.O. ４ , Li ７ La ３ Zr ２ O １２ The content of the ion-conductive solid of the present disclosure in the electrolyte of the all-solid-state battery of the present disclosure is not particularly limited, and is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and particularly preferably 100% by mass.

[0039] The all-solid-state battery of the present disclosure has a positive electrode. The positive electrode may contain a positive electrode active material, or may contain the positive electrode active material and the ion-conducting solid of the present disclosure. As the positive electrode active material, known positive electrode active materials such as sulfides containing transition metal elements and oxides containing lithium and transition metal elements can be used without particular limitation. For example, LiNiVO ４ , LiCoPO ４ , LiCoVO ４ , LiMn １．６ Ni ０．４ O ４ , LiMn ２ O ４ , LiCoO ２ , Fe ２ (SO ４ ) ３ , LiFePO ４ , LiNi １／３ Mn １／３ Co １／３ O ２ , LiNi １／２ Mn １／２ O ２ , LiNiO ２ , Li １＋ｘ (Fe, Mn, Co) １－ｘ O ２ , LiNi ０．８ Co ０．１５ Al ０．０５ O ２ The positive electrode may further contain a binder, a conductive agent, etc. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, and polyvinyl alcohol. Examples of the conductive agent include natural graphite, artificial graphite, acetylene black, and ethylene black.

[0040] The all-solid-state battery of the present disclosure has a negative electrode. The negative electrode may contain a negative electrode active material, or may contain the negative electrode active material and the ion-conductive solid of the present disclosure. As the negative electrode active material, known negative electrode active materials such as inorganic compounds such as lithium, lithium alloys, and tin compounds, carbonaceous materials capable of absorbing and releasing lithium ions, and conductive polymers can be used without any particular limitation. For example, Li ４ Ti ５ O １２Furthermore, the negative electrode may contain a binder, a conductive agent, etc. As the binder and the conductive agent, the same materials as those exemplified for the positive electrode can be used.

[0041] Here, the expression "including" an electrode active material means that the electrode has the electrode active material as a component, element, or property. For example, both cases where the electrode contains the electrode active material within the electrode and cases where the electrode active material is applied to the surface of the electrode fall under the category of "including."

[0042] The positive electrode and the negative electrode can be obtained by known methods such as mixing raw materials, molding, and heat treatment. It is believed that this allows the ion-conductive solid to penetrate into gaps between the electrode active materials, making it easier to secure a conduction path for lithium ions. The ion-conductive solid of the present disclosure can be produced by heat treatment at a lower temperature than conventional techniques, which is believed to suppress the formation of a high-resistance phase that occurs when the ion-conductive solid reacts with the electrode active material.

[0043] The positive electrode and the negative electrode may each have a current collector. Known current collectors such as aluminum, titanium, stainless steel, nickel, iron, baked carbon, conductive polymers, and conductive glass can be used as the current collector. In addition, for the purpose of improving adhesion, conductivity, oxidation resistance, and the like, a current collector obtained by treating the surface of aluminum, copper, or the like with carbon, nickel, titanium, silver, or the like can be used.

[0044] The all-solid-state battery of the present disclosure can be obtained by a known method, for example, by stacking a positive electrode, a solid electrolyte, and a negative electrode, molding, heat treatment, etc. The ion-conductive solid of the present disclosure can be produced by heat treatment at a lower temperature than conventional techniques, which is thought to suppress the formation of a high-resistance phase that occurs when the ion-conductive solid reacts with the electrode active material, and is thought to enable the production of an all-solid-state battery with excellent output characteristics.

[0045] Next, the methods for measuring the composition and physical properties according to the present disclosure will be described. -Methods for identifying and analyzing contained metals. Composition analysis of ion-conductive solids is performed using wavelength-dispersive X-ray fluorescence spectroscopy (hereinafter also referred to as XRF) on samples solidified by pressure molding. However, if analysis is difficult due to particle size effects, etc., it is recommended to vitrify the ion-conductive solid using the glass bead method and then perform composition analysis by XRF. Furthermore, if the yttrium peak and contained metal peak overlap in XRF, it is recommended to perform composition analysis by inductively coupled plasma atomic emission spectroscopy (ICP-AES). For XRF, a ZSX Primus II analyzer manufactured by Rigaku Corporation is used. The analysis conditions are as follows: Rh is used as the anode of the X-ray tube; the analysis diameter is 10 mm; the analysis range is 17° to 81°; the step is 0.01°; and the scan speed is 5 sec / step. Light elements are measured using a proportional counter, and heavy elements are measured using a scintillation counter. Elements are identified based on the peak positions of the spectrum obtained by XRF, and the molar concentration ratios a, b, c, and d are calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

[0046] Examples in which the ion-conductive solid of the present disclosure was specifically produced and evaluated will be described below as examples, although the present disclosure is not limited to the following examples.

[0047] [Example 1] Primary firing process Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), and Nb ２ O ５(Mitsui Mining & Smelting, purity 99.9%) was used as the raw material. Each raw material was weighed in stoichiometric amounts so that d was the value listed in Table 1, and mixed for 30 minutes at a disk rotation speed of 300 rpm in a Fritsch planetary mill P-7. A zirconia φ5 mm ball and a 45 mL container were used for the planetary mill. After mixing, the mixed powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems, and sintered in an air atmosphere. The heating temperature was 650 ° C, and the holding time was 720 minutes. The obtained ion-conductive solid containing the oxide was pulverized for 180 minutes at a disk rotation speed of 230 rpm in a Fritsch planetary mill P-7 to produce a powder of an ion-conductive solid containing the oxide. The powder of the ion-conductive solid containing the oxide obtained above was molded and subjected to secondary firing to produce a sintered body of the ion-conductive solid containing the oxide of Example 1. For molding, the powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems. The secondary firing was carried out in an air atmosphere at a heating temperature of 650°C and a holding time of 720 minutes.

[0048] [Example 2] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), and CeO ２ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 2 was produced in the same process as Example 1, except that each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 1.

[0049] [Example 3] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３(manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), ZrO ２ (Nippon Denko, purity 99.9%), CeO ２ (Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 3 was produced in the same manner as in Example 1, except that sintered body (manufactured by Mitsui Mining & Smelting Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 1.

[0050] Example 4 A sintered body of an ion-conductive solid containing the oxide of Example 4 was produced in the same process as Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so as to obtain the values ​​shown in Table 1.

[0051] [Example 5] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and HfO ２ A sintered body of an ion-conductive solid containing the oxide of Example 5 was produced in the same manner as in Example 1, except that sintered body (manufactured by New Metals, purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 1.

[0052] Example 6 A sintered body of an ion-conductive solid containing the oxide of Example 6 was produced in the same manner as in Example 1, except that each raw material used in the above example was weighed out in a stoichiometric amount so that c was the value shown in Table 1.

[0053] Example 7 A sintered body of an ion-conductive solid containing the oxide of Example 7 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 1.

[0054] [Example 8] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３(Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), In ２ O ３ (Manufactured by Shinko Kagaku Kogyo, purity 99% by mass), SnO ２ (Mitsuwa Chemicals, purity 99.9%) and CeO ２ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 8 was produced in the same process as in Example 1, except that each raw material was weighed out in stoichiometric amounts so that b and c had the values ​​shown in Table 1.

[0055] Example 9 A sintered body of an ion-conductive solid containing the oxide of Example 9 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0056] [Example 10] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Fe ２ O ３ (Wako Pure Chemical Industries, Ltd., purity 95.0% by mass) and TiO ２ A sintered body of an ion-conductive solid containing the oxide of Example 10 was produced in the same manner as in Example 1, except that sintered body (manufactured by Toho Titanium, purity 99%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0057] Example 11 A sintered body of an ion-conductive solid containing the oxide of Example 11 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0058] [Example 12] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), B ２ O ３ (manufactured by Wako Pure Chemical Industries, purity 99.9%), Ho２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Lu ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 12 was produced in the same manner as in Example 1, except that sintered body (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b was the value shown in Table 1.

[0059] [Example 13] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), MgO (manufactured by Ube Material Industries, purity 99.0% by mass), and CeO ２ A sintered body of an ion-conductive solid containing the oxide of Example 13 was produced in the same manner as in Example 1, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that a and c had the values ​​shown in Table 1.

[0060] [Example 14] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), La ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 14 was produced by the same process as in Example 1, except that ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0% by mass), and CaO (manufactured by Kanto Chemical, purity 97.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1.

[0061] [Example 15] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３(Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), La ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 15 was produced in the same manner as in Example 1, except that sintered bodies of SiO2 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0062] [Example 16] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 16 was produced in the same manner as in Example 1, except that sintered bodies of MnO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0063] [Example 17] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tm ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 17 was produced in the same process as in Example 1, except that sintered bodies of MnO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0064] Example 18 A sintered body of an ion-conductive solid containing the oxide of Example 18 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 1.

[0065] [Example 19] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), In ２ O ３ (manufactured by Shinko Kagaku Kogyo, purity 99% by mass), Nb ２ O ５ (Mitsui Mining & Smelting Co., Ltd., purity 99.9%) and Ta ２ O ５ (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 19 was produced in the same process as in Example 1, except that each raw material was weighed out in stoichiometric amounts so that b and d had the values ​​shown in Table 1.

[0066] [Example 20] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Pr ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 20 was produced in the same manner as in Example 1, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b was the value shown in Table 1.

[0067] Example 21 A sintered body of an ion-conductive solid containing the oxide of Example 21 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d had the values ​​shown in Table 1.

[0068] [Example 22] Li ２ CO３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Sm ２ O ３ (manufactured by Wako Pure Chemical Industries, purity 99.9% by mass), HfO ２ (manufactured by New Metals, purity 99.9%) and Ta ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 22 was produced in the same manner as in Example 1, except that sintered body (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 1.

[0069] [Example 23] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Nd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Sm ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 23 was produced in the same manner as in Example 1, except that ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1.

[0070] Example 24 A sintered body of an ion-conductive solid containing the oxide of Example 24 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0071] [Example 25] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Eu ２ O ３ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 25 was produced in the same process as in Example 1, except that each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 1.

[0072] [Example 26] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Eu ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 26 was produced in the same manner as in Example 1, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0073] Example 27 A sintered body of an ion-conductive solid containing the oxide of Example 27 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0074] [Example 28] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Gd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Dy ２ O ３An ion-conductive solid sintered body containing the oxide of Example 28 was produced in the same manner as in Example 1, except that sintered bodies containing the oxide of Example 28 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and CaO (manufactured by Kanto Chemical, purity 99.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0075] Example 29 A sintered body of an ion-conductive solid containing the oxide of Example 29 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0076] Example 30 A sintered body of an ion-conductive solid containing an oxide of Example 30 was produced in the same manner as in Example 1, except that each raw material used in the above example was weighed out in a stoichiometric amount so that b and c had the values ​​shown in Table 1.

[0077] Example 31 A sintered body of an ion-conductive solid containing the oxide of Example 31 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in a stoichiometric amount so that b was the value shown in Table 1.

[0078] [Example 32] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 32 was produced in the same manner as in Example 1, except that sintered bodies containing the oxide of Example 32 were prepared using NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass), and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1.

[0079] [Example 33] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Ho ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 33 was produced in the same manner as in Example 1, except that BaO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0080] Example 34 A sintered body of an ion-conductive solid containing the oxide of Example 34 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 1.

[0081] [Example 35] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tm ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 35 was produced in the same process as in Example 1, except that SrO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and SrO (manufactured by Kojundo Chemical Laboratory, purity 98% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b had the values ​​shown in Table 1.

[0082] Example 36 A sintered body of an ion-conductive solid containing the oxide of Example 36 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 1.

[0083] Example 37 A sintered body of an ion-conductive solid containing the oxide of Example 37 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 1.

[0084] Example 38 A sintered body of an ion-conductive solid containing the oxide of Example 38 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 1.

[0085] Example 39 A sintered body of an ion-conductive solid containing the oxide of Example 39 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 1.

[0086] Example 40 A sintered body of an ion-conductive solid containing the oxide of Example 40 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 1.

[0087] Example 41 A sintered body of an ion-conductive solid containing the oxide of Example 41 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 1.

[0088] Example 42 A sintered body of an ion-conductive solid containing an oxide of Example 42 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 1.

[0089] [Example 43] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Lu ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Sc ２ O ３A sintered body of an ion-conductive solid containing the oxide of Example 26 was produced in the same manner as in Example 1, except that sintered body (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b was the value shown in Table 1.

[0090] Example 44 A sintered body of an ion-conductive solid containing the oxide of Example 44 was produced by the same process as in Example 1, except that each raw material used in the above Examples was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and the disk rotation speed during grinding was set to 300 rpm.

[0091] Example 45 A sintered body of an ion-conductive solid containing the oxide of Example 45 was produced by the same process as in Example 1, except that each raw material used in the above Examples was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and the disk rotation speed during grinding was set to 300 rpm.

[0092] Example 46 A sintered body of an ion-conductive solid containing the oxide of Example 46 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and the disk rotation speed during grinding was set to 300 rpm.

[0093] Example 47 A sintered body of an ion-conductive solid containing the oxide of Example 47 was produced by the same process as in Example 1, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 1, the disk rotation speed during grinding was set to 150 rpm, and the grinding time was set to 60 minutes.

[0094] [Comparative Example 1] The raw material Lu in Example 1 ２ O ３ Y ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Comparative Example 1 was produced in the same process as in Example 1, except that the starting material was changed to the above, and each raw material was weighed out in a stoichiometric amount so that d was the value shown in Table 1.

[0095] [Comparative Example 2] The raw material Lu in Example 2 ２ O ３ Y ２ O ３A sintered body of an ion-conductive solid containing the oxide of Comparative Example 2 was produced in the same process as in Example 2, except that the composition ratio was changed to 1 / 2 and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 1.

[0096] [Comparative Example 3] The raw material Lu in Example 3 ２ O ３ Y ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Comparative Example 3 was produced in the same process as in Example 3, except that the composition ratio was changed to 1 / 2 and that the raw materials were weighed out in stoichiometric amounts so that c and d were the values ​​shown in Table 1.

[0097] [Example 101] Primary firing step Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), and Nb ２ O ５ (Mitsui Mining & Smelting, purity 99.9%) was used as the raw material. Each raw material was weighed in stoichiometric amounts so that d was the value listed in Table 2, and mixed for 30 minutes at a disk rotation speed of 300 rpm in a Fritsch planetary mill P-7. A zirconia φ5 mm ball and a 45 mL container were used for the planetary mill. After mixing, the mixed powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems, and sintered in an air atmosphere. The heating temperature was 650 ° C, and the holding time was 720 minutes. The obtained ion-conductive solid containing the oxide was pulverized for 180 minutes at a disk rotation speed of 230 rpm in a Fritsch planetary mill P-7 to produce a powder of an ion-conductive solid containing the oxide. The powder of the ion-conductive solid containing the oxide obtained above was molded and subjected to secondary firing to produce a sintered body of the ion-conductive solid containing the oxide of Example 101. For molding, the powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems. The secondary firing was carried out in an air atmosphere, with a heating temperature of 650°C and a holding time of 720 minutes.

[0098] [Example 102] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), and CeO ２ An ion-conductive solid sintered body containing the oxide of Example 102 was produced in the same manner as in Example 101, except that sintered bodies containing the oxide of Example 102 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) were used as raw materials and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 2.

[0099] [Example 103] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), ZrO ２ (Nippon Denko, purity 99.9%), CeO ２ (Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 103 was produced in the same manner as in Example 101, except that sintered body (manufactured by Mitsui Mining & Smelting Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 2.

[0100] Example 104 A sintered body of an ion-conductive solid containing an oxide of Example 104 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so as to obtain the values ​​shown in Table 2.

[0101] [Example 105] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and HfO ２A sintered body of an ion-conductive solid containing the oxide of Example 105 was produced in the same manner as in Example 101, except that sintered body (manufactured by New Metals, purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 2.

[0102] Example 106 A sintered body of an ion-conductive solid containing the oxide of Example 106 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in a stoichiometric amount so that c was the value shown in Table 2.

[0103] Example 107 A sintered body of an ion-conductive solid containing the oxide of Example 107 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d were the values ​​shown in Table 2.

[0104] [Example 108] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), In ２ O ３ (manufactured by Shinko Chemical Industry, purity 99% by mass) and SnO ２ A sintered body of an ion-conductive solid containing the oxide of Example 108 was produced in the same manner as in Example 101, except that sintered body (manufactured by Mitsuwa Chemicals, purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0105] Example 109 A sintered body of an ion-conductive solid containing the oxide of Example 109 was produced by the same process as in Example 101, except that each raw material used in the above examples was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0106] [Example 110] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３(manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Fe ２ O ３ (Wako Pure Chemical Industries, Ltd., purity 95.0% by mass) and TiO ２ A sintered body of an ion-conductive solid containing the oxide of Example 110 was produced in the same manner as in Example 101, except that sintered body (manufactured by Toho Titanium, purity 99%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0107] Example 111 A sintered body of an ion-conductive solid containing the oxide of Example 111 was produced in the same manner as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0108] [Example 112] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), MgO (manufactured by Ube Material Industries, purity 99.0% by mass), and CeO ２ A sintered body of an ion-conductive solid containing the oxide of Example 112 was produced in the same manner as in Example 101, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that a and c were the values ​​shown in Table 2.

[0109] [Example 113] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), La ２ O ３An ion-conductive solid sintered body containing the oxide of Example 113 was produced in the same process as in Example 101, except that SiO2 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0% by mass), and CaO (manufactured by Kanto Chemical, purity 97.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0110] [Example 114] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Lu ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 114 was produced in the same process as in Example 101, except that sintered bodies of MnO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0111] [Example 115] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 115 was produced in the same manner as in Example 101, except that SiO2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0112] [Example 116] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tm ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 116 was produced in the same process as in Example 101, except that BaO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0113] [Example 117] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), SnO ２ (Mitsuwa Chemicals, purity 99.9%) and Nb ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 117 was produced in the same manner as in Example 101, except that sintered body (manufactured by Mitsui Mining & Smelting Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 2.

[0114] [Example 118] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), In ２ O ３ (manufactured by Shinko Kagaku Kogyo, purity 99% by mass), Nb ２ O ５ (Mitsui Mining & Smelting Co., Ltd., purity 99.9%) and Ta ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 118 was produced in the same manner as in Example 101, except that sintered body (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 2.

[0115] [Example 119] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Pr ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 119 was produced in the same manner as in Example 101, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) was used as a raw material and each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 2.

[0116] Example 120 A sintered body of an ion-conductive solid containing the oxide of Example 120 was produced in the same manner as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 2.

[0117] [Example 121] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Sm ２ O ３ (manufactured by Wako Pure Chemical Industries, purity 99.9% by mass), HfO ２ (manufactured by New Metals, purity 99.9%) and Ta ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 121 was produced in the same manner as in Example 101, except that sintered body (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 2.

[0118] [Example 122] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３(manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Nd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Sm ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 122 was produced in the same manner as in Example 101, except that ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0119] Example 123 A sintered body of an ion-conductive solid containing the oxide of Example 123 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0120] [Example 124] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Eu ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 124 was produced in the same manner as in Example 101, except that sintered body of an ion-conductive solid containing the oxide of Example 124 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) was used as a raw material and each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 2.

[0121] [Example 125] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Eu ２ O ３An ion-conductive solid sintered body containing the oxide of Example 125 was produced in the same manner as in Example 101, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0122] Example 126 A sintered body of an ion-conductive solid containing the oxide of Example 126 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0123] [Example 127] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Gd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Dy ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 127 was produced in the same manner as in Example 101, except that sintered bodies containing the oxide of Example 127 were prepared by using stoichiometric amounts of ZnO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and CaO (manufactured by Kanto Chemical, purity 99.0% by mass) as raw materials, and that the raw materials were weighed out so that a and b were the values ​​shown in Table 2.

[0124] Example 128 A sintered body of an ion-conductive solid containing the oxide of Example 128 was produced in the same manner as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0125] Example 129 A sintered body of an ion-conductive solid containing the oxide of Example 129 was produced in the same manner as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0126] Example 130 A sintered body of an ion-conductive solid containing the oxide of Example 130 was produced in the same manner as in Example 101, except that each raw material used in the above example was weighed out in a stoichiometric amount so that b was the value shown in Table 2.

[0127] [Example 131] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 131 was produced in the same process as in Example 101, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass), and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0128] Example 132 A sintered body of an ion-conductive solid containing an oxide of Example 132 was produced in the same manner as in Example 101, except that each raw material used in the above examples was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 2.

[0129] [Example 133] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tm ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 133 was produced in the same process as in Example 101, except that SrO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and SrO (manufactured by Kojundo Chemical Laboratory, purity 98% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2.

[0130] Example 134 A sintered body of an ion-conductive solid containing the oxide of Example 134 was produced by the same process as in Example 101, except that each raw material used in the above examples was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 2.

[0131] Example 135 A sintered body of an ion-conductive solid containing the oxide of Example 135 was produced in the same manner as in Example 101, except that each raw material used in the above examples was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 2.

[0132] Example 136 A sintered body of an ion-conductive solid containing the oxide of Example 136 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 2.

[0133] Example 137 A sintered body of an ion-conductive solid containing the oxide of Example 137 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 2.

[0134] Example 138 A sintered body of an ion-conductive solid containing the oxide of Example 138 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 2.

[0135] Example 139 A sintered body of an ion-conductive solid containing the oxide of Example 139 was produced in the same manner as in Example 101, except that each raw material used in the above examples was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 2.

[0136] Example 140 A sintered body of an ion-conductive solid containing the oxide of Example 140 was produced by the same process as in Example 101, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 2.

[0137] [Example 141] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO３ (Kanto Chemical, purity 99.5%), Ho ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Sc ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 141 was produced in the same process as in Example 101, except that sintered body (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) was used as a raw material and each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 2.

[0138] Example 142 A sintered body of an ion-conductive solid containing the oxide of Example 142 was produced by the same process as in Example 101, except that each raw material used in the above Examples was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2, and the disk rotation speed during grinding was set to 300 rpm.

[0139] Example 143 A sintered body of an ion-conductive solid containing the oxide of Example 143 was produced by the same process as in Example 101, except that each raw material used in the above Examples was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2, and the disk rotation speed during grinding was set to 300 rpm.

[0140] Example 144 A sintered body of an ion-conductive solid containing the oxide of Example 144 was produced by the same process as in Example 101, except that each raw material used in the above Examples was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 2, and the disk rotation speed during grinding was set to 300 rpm.

[0141] [Example 201] Primary firing step Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), and Nb ２ O ５(Mitsui Mining & Smelting Co., Ltd., purity 99.9%) was used as the raw material. Each raw material was weighed in stoichiometric amounts so that d was the value listed in Table 3, and mixed for 30 minutes at a disk rotation speed of 300 rpm in a Fritsch planetary mill P-7. A zirconia φ5 mm ball and a 45 mL container were used for the planetary mill. After mixing, the mixed powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems, and sintered in an air atmosphere. The heating temperature was 650 ° C, and the holding time was 720 minutes. The obtained ion-conductive solid containing the oxide was pulverized for 180 minutes at a disk rotation speed of 230 rpm in a Fritsch planetary mill P-7 to produce a powder of an ion-conductive solid containing the oxide. The powder of the ion-conductive solid containing the oxide obtained above was molded and subjected to secondary firing to produce a sintered body of the ion-conductive solid containing the oxide of Example 1. For molding, the powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems. The secondary firing was carried out in an air atmosphere at a heating temperature of 650°C and a holding time of 720 minutes.

[0142] [Example 202] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), and CeO ２ An ion-conductive solid sintered body containing the oxide of Example 202 was produced in the same manner as in Example 201, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 3.

[0143] [Example 203] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), ZrO ２(Nippon Denko, purity 99.9%), CeO ２ (Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 203 was produced in the same manner as in Example 201, except that sintered body (manufactured by Mitsui Mining & Smelting Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 3.

[0144] Example 204 A sintered body of an ion-conductive solid containing the oxide of Example 204 was produced using the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so as to obtain the values ​​shown in Table 3.

[0145] [Example 205] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and HfO ２ An ion-conductive solid sintered body containing the oxide of Example 205 was produced in the same manner as in Example 201, except that sintered body (manufactured by New Metals, purity 99.9%) was used as the raw material and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 3.

[0146] Example 206 A sintered body of an ion-conductive solid containing the oxide of Example 206 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in a stoichiometric amount so that c was the value shown in Table 3.

[0147] Example 207 A sintered body of an ion-conductive solid containing the oxide of Example 207 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d were the values ​​shown in Table 3.

[0148] [Example 208] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), In ２ O ３ (manufactured by Shinko Chemical Industry, purity 99% by mass) and SnO ２ A sintered body of an ion-conductive solid containing the oxide of Example 208 was produced in the same manner as in Example 201, except that sintered body (manufactured by Mitsuwa Chemicals, purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0149] Example 209 A sintered body of an ion-conductive solid containing the oxide of Example 209 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0150] [Example 210] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Fe ２ O ３ (Wako Pure Chemical Industries, Ltd., purity 95.0% by mass) and TiO ２ A sintered body of an ion-conductive solid containing the oxide of Example 210 was produced in the same process as in Example 201, except that sintered body (manufactured by Toho Titanium, purity 99%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0151] Example 211 A sintered body of an ion-conductive solid containing the oxide of Example 211 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0152] [Example 212] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0% by mass), and CeO ２ A sintered body of an ion-conductive solid containing the oxide of Example 212 was produced in the same manner as in Example 201, except that sintered body of an ion-conductive solid containing the oxide of Example 212 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that a and c were the values ​​shown in Table 3.

[0153] [Example 213] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), La ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 213 was produced in the same process as in Example 201, except that SiO2 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0% by mass), and CaO (manufactured by Kanto Chemical, purity 97.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0154] [Example 214] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Lu ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 214 was produced in the same manner as in Example 201, except that sintered bodies containing the oxide of Example 214 (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0155] [Example 215] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３(Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 215 was produced in the same manner as in Example 201, except that SiO2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0156] [Example 216] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tm ２ O ３ A sintered body of an ion-conductive solid containing the oxide of Example 216 was produced in the same process as in Example 201, except that sintered bodies of MnO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0157] Example 217 A sintered body of an ion-conductive solid containing the oxide of Example 217 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d were the values ​​shown in Table 3.

[0158] [Example 218] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), In ２ O ３ (manufactured by Shinko Kagaku Kogyo, purity 99% by mass), Nb ２ O ５ (Mitsui Mining & Smelting Co., Ltd., purity 99.9%) and Ta ２ O ５A sintered body of an ion-conductive solid containing the oxide of Example 218 was produced in the same manner as in Example 201, except that sintered body (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 3.

[0159] [Example 219] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and Pr ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 219 was produced in the same manner as in Example 201, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b was the value shown in Table 3.

[0160] Example 220 A sintered body of an ion-conductive solid containing the oxide of Example 220 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 3.

[0161] [Example 221] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Sm ２ O ３ (manufactured by Wako Pure Chemical Industries, purity 99.9% by mass), HfO ２ (manufactured by New Metals, purity 99.9%) and Ta ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 221 was produced in the same manner as in Example 201, except that sintered body (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 3.

[0162] [Example 222] Li ２CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Nd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Sm ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 222 was produced in the same manner as in Example 201, except that ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0163] Example 223 A sintered body of an ion-conductive solid containing the oxide of Example 223 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0164] [Example 224] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and Eu ２ O ３ (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 224 was produced in the same process as in Example 201, except that each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 3.

[0165] [Example 225] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Eu ２ O ３An ion-conductive solid sintered body containing the oxide of Example 225 was produced in the same manner as in Example 201, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0166] Example 226 A sintered body of an ion-conductive solid containing the oxide of Example 226 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0167] [Example 227] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Gd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Dy ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 227 was produced in the same manner as in Example 201, except that sintered bodies containing the oxide of Example 227 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and CaO (manufactured by Kanto Chemical, purity 99.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0168] Example 228 A sintered body of an ion-conductive solid containing the oxide of Example 228 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0169] Example 229 A sintered body of an ion-conductive solid containing the oxide of Example 229 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 3.

[0170] Example 230 A sintered body of an ion-conductive solid containing the oxide of Example 230 was produced in the same manner as in Example 201, except that each raw material used in the above example was weighed out in a stoichiometric amount so that b was the value shown in Table 3.

[0171] [Example 231] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 231 was produced in the same process as in Example 201, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass), and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0172] [Example 232] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Ho ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 232 was produced in the same process as in Example 201, except that SrO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) and SrO (manufactured by Kojundo Chemical Laboratory, purity 98% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 3.

[0173] Example 233 A sintered body of an ion-conductive solid containing the oxide of Example 233 was produced in the same manner as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 3.

[0174] Example 234 A sintered body of an ion-conductive solid containing the oxide of Example 234 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 3.

[0175] Example 235 A sintered body of an ion-conductive solid containing the oxide of Example 235 was produced in the same manner as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 3.

[0176] Example 236 A sintered body of an ion-conductive solid containing the oxide of Example 236 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 3.

[0177] Example 237 A sintered body of an ion-conductive solid containing the oxide of Example 237 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 3.

[0178] Example 238 A sintered body of an ion-conductive solid containing the oxide of Example 238 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 3.

[0179] [Example 239] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Er ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and Sc ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 239 was produced in the same process as in Example 201, except that each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 3.

[0180] Example 240 A sintered body of an ion-conductive solid containing the oxide of Example 240 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3, and the disk rotation speed during grinding was set to 300 rpm.

[0181] Example 241 A sintered body of an ion-conductive solid containing the oxide of Example 241 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3, and the disk rotation speed during grinding was set to 300 rpm.

[0182] Example 242 A sintered body of an ion-conductive solid containing the oxide of Example 242 was produced by the same process as in Example 201, except that each raw material used in the above example was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3, and the disk rotation speed during grinding was set to 300 rpm.

[0183] [Example 301] Primary firing step Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), and Nb ２ O ５(Mitsui Mining & Smelting, purity 99.9%) was used as the raw material. Each raw material was weighed in stoichiometric amounts so that d was the value listed in Table 4, and mixed for 30 minutes at a disk rotation speed of 300 rpm in a Fritsch planetary mill P-7. A zirconia φ5 mm ball and a 45 mL container were used for the planetary mill. After mixing, the mixed powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems, and sintered in an air atmosphere. The heating temperature was 650 ° C, and the holding time was 720 minutes. The obtained ion-conductive solid containing the oxide was pulverized for 180 minutes at a disk rotation speed of 230 rpm in a Fritsch planetary mill P-7 to produce a powder of an ion-conductive solid containing the oxide. The powder of the ion-conductive solid containing the oxide obtained above was molded and subjected to secondary firing to produce a sintered body of the ion-conductive solid containing the oxide of Example 301. For molding, the powder was cold uniaxially molded at 147 MPa using a 100 kN electric press P3052-10 manufactured by NPA Systems. The secondary firing was carried out in an air atmosphere, with a heating temperature of 650°C and a holding time of 720 minutes.

[0184] [Example 302] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), and CeO ２ An ion-conductive solid sintered body containing the oxide of Example 302 was produced in the same manner as in Example 301, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 4.

[0185] [Example 303] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), ZrO ２(Nippon Denko, purity 99.9%), CeO ２ (Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 303 was produced in the same manner as in Example 301, except that sintered body (manufactured by Mitsui Mining & Smelting Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that c and d had the values ​​shown in Table 4.

[0186] Example 304 A sintered body of an ion-conductive solid containing an oxide of Example 304 was produced by the same process as Example 301, except that each raw material used in the above example was weighed out in a stoichiometric amount so as to obtain the values ​​shown in Table 4.

[0187] [Example 305] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and HfO ２ An ion-conductive solid sintered body containing the oxide of Example 305 was produced in the same manner as in Example 301, except that sintered body (manufactured by New Metals, purity 99.9%) was used as the raw material and each raw material was weighed out in stoichiometric amounts so that c was the value shown in Table 4.

[0188] Example 306 A sintered body of an ion-conductive solid containing the oxide of Example 306 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in a stoichiometric amount so that c was the value shown in Table 4.

[0189] Example 307 A sintered body of an ion-conductive solid containing the oxide of Example 307 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d were the values ​​shown in Table 4.

[0190] [Example 308] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３(Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), In ２ O ３ (manufactured by Shinko Chemical Industry, purity 99% by mass) and SnO ２ A sintered body of an ion-conductive solid containing the oxide of Example 308 was produced in the same manner as in Example 301, except that sintered body (manufactured by Mitsuwa Chemicals, purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0191] Example 309 A sintered body of an ion-conductive solid containing the oxide of Example 309 was produced in the same manner as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0192] [Example 310] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Fe ２ O ３ (Wako Pure Chemical Industries, Ltd., purity 95.0% by mass) and TiO ２ A sintered body of an ion-conductive solid containing the oxide of Example 310 was produced in the same process as in Example 301, except that sintered body (manufactured by Toho Titanium, purity 99%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0193] Example 311 A sintered body of an ion-conductive solid containing the oxide of Example 311 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0194] [Example 312] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass), MgO (manufactured by Ube Material Industries, purity 99.0% by mass), and CeO ２ A sintered body of an ion-conductive solid containing the oxide of Example 312 was produced in the same manner as in Example 301, except that sintered body of an ion-conductive solid containing the oxide of Example 312 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that a and c were the values ​​shown in Table 4.

[0195] [Example 313] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), La ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 313 was produced in the same process as in Example 301, except that SiO2 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0% by mass), and CaO (manufactured by Kanto Chemical, purity 97.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0196] [Example 314] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Lu ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 314 was produced in the same manner as in Example 301, except that sintered bodies containing the oxide of Example 314 (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0197] [Example 315] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 315 was produced in the same manner as in Example 301, except that SiO2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) and MnO (manufactured by Kanto Chemical, purity 80.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0198] Example 316 A sintered body of an ion-conductive solid containing the oxide of Example 316 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that c and d were the values ​​shown in Table 4.

[0199] [Example 317] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), In ２ O ３ (manufactured by Shinko Kagaku Kogyo, purity 99% by mass), Nb ２ O ５ (Mitsui Mining & Smelting Co., Ltd., purity 99.9%) and Ta ２ O ５ A sintered body of an ion-conductive solid containing the oxide of Example 317 was produced in the same manner as in Example 301, except that sintered body (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 4.

[0200] [Example 318] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Pr ２ O ３An ion-conductive solid sintered body containing the oxide of Example 318 was produced in the same manner as in Example 301, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b was the value shown in Table 4.

[0201] Example 319 A sintered body of an ion-conductive solid containing the oxide of Example 319 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 4.

[0202] [Example 320] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Sm ２ O ３ (manufactured by Wako Pure Chemical Industries, purity 99.9% by mass), HfO ２ (manufactured by New Metals, purity 99.9%) and Ta ２ O ５ (manufactured by Kanto Chemical, purity 99% by mass) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 320 was produced in the same process as in Example 301, except that each raw material was weighed out in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 4.

[0203] [Example 321] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Nd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Sm ２ O ３An ion-conductive solid sintered body containing the oxide of Example 321 was produced in the same process as in Example 301, except that ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by mass) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0204] Example 322 A sintered body of an ion-conductive solid containing the oxide of Example 322 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0205] [Example 323] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Eu ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 323 was produced in the same manner as in Example 301, except that sintered body (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) was used as a raw material and each raw material was weighed out in stoichiometric amounts so that b was the value shown in Table 4.

[0206] [Example 324] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Eu ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 324 was produced in the same manner as in Example 301, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0207] Example 325 A sintered body of an ion-conductive solid containing the oxide of Example 325 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0208] [Example 326] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Gd ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Dy ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 326 was produced in the same manner as in Example 301, except that sintered bodies containing the oxide of Example 326 were prepared using stoichiometric amounts of ZnO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and CaO (manufactured by Kanto Chemical, purity 99.0% by mass) as raw materials, and a and b were calculated as shown in Table 4.

[0209] Example 327 A sintered body of an ion-conductive solid containing the oxide of Example 327 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0210] Example 328 A sintered body of an ion-conductive solid containing the oxide of Example 328 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0211] Example 329 A sintered body of an ion-conductive solid containing the oxide of Example 329 was produced in the same manner as in Example 301, except that each raw material used in the above example was weighed out in a stoichiometric amount so that b was the value shown in Table 4.

[0212] [Example 330] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３(Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 330 was produced in the same process as in Example 301, except that NiO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0% by mass), and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0213] [Example 331] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Tb ２ O ３ (Shin-Etsu Chemical Co., Ltd., purity 99.9% by mass), Ho ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 331 was produced in the same process as in Example 301, except that BaO (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0214] Example 332 A sintered body of an ion-conductive solid containing the oxide of Example 332 was produced in the same manner as in Example 301, except that each raw material used in the above example was weighed out in a stoichiometric amount so that b, c, and d were the values ​​shown in Table 4.

[0215] [Example 333] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３ (manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Ho ２ O ３(manufactured by Kojundo Kagaku Kenkyusho, purity 99.9% by mass), Er ２ O ３ An ion-conductive solid sintered body containing the oxide of Example 333 was produced in the same process as in Example 301, except that SrO (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass) and SrO (manufactured by Kojundo Chemical Laboratory, purity 98% by mass) were used as raw materials, and each raw material was weighed out in stoichiometric amounts so that a and b were the values ​​shown in Table 4.

[0216] Example 334 A sintered body of an ion-conductive solid containing the oxide of Example 334 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and c were the values ​​shown in Table 4.

[0217] Example 335 A sintered body of an ion-conductive solid containing the oxide of Example 335 was produced in the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 4.

[0218] Example 336 A sintered body of an ion-conductive solid containing the oxide of Example 336 was produced in the same manner as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 4.

[0219] Example 337 A sintered body of an ion-conductive solid containing the oxide of Example 337 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 4.

[0220] Example 338 A sintered body of an ion-conductive solid containing the oxide of Example 338 was produced in the same manner as in Example 301, except that each raw material used in the above example was weighed out in stoichiometric amounts so that b and d were the values ​​shown in Table 4.

[0221] [Example 339] Li ２ CO ３ (Nacalai Tesque, purity 99.0% by mass), H ３ BO ３ (Kanto Chemical, purity 99.5%), Tm ２ O ３(manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) and Sc ２ O ３ (manufactured by Kojundo Chemical Laboratory, purity 99.9% by mass) was used as a raw material, and a sintered body of an ion-conductive solid containing the oxide of Example 339 was produced in the same process as in Example 301, except that each raw material was weighed out in a stoichiometric amount so that b was the value shown in Table 4.

[0222] Example 340 A sintered body of an ion-conductive solid containing the oxide of Example 340 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4, and the disk rotation speed during grinding was set to 300 rpm.

[0223] Example 341 A sintered body of an ion-conductive solid containing the oxide of Example 341 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4, and the disk rotation speed during grinding was set to 300 rpm.

[0224] Example 342 A sintered body of an ion-conductive solid containing the oxide of Example 342 was produced by the same process as in Example 301, except that each raw material used in the above example was weighed in a stoichiometric amount so that a and b were the values ​​shown in Table 4, and the disk rotation speed during grinding was set to 300 rpm.

[0225] [Comparative Example 4] Tm of raw materials in Example 4 ２ O ３ Sc ２ O ３ (Sc ３＋ When the ionic radius of the sintered body was changed to 0.87 Å and the sintered body was produced by the same process as in Example 4, it was not possible to obtain a crystal structure similar to that of Example 4. The impedance of the obtained sintered body was measured by the method described below, but the resistance of the sintered body could not be measured and the ionic conductivity could not be obtained as a numerical value.

[0226] [Comparative Example 5] Tm of raw materials in Example 4 ２ O ３ Fe ２ O ３ (Fe ３＋When the ionic radius of the sintered body was changed to 0.78 Å and the sintered body was produced by the same process as in Example 4, it was not possible to obtain a crystal structure similar to that of Example 4. The impedance of the obtained sintered body was measured by the method described below, but the resistance of the sintered body could not be measured and the ionic conductivity could not be obtained as a numerical value.

[0227] [Comparative Example 6] Tm of raw materials in Example 4 ２ O ３ La ２ O ３ (La ３＋ When the ionic radius of the sintered body was changed to 1.16 Å and the sintered body was produced by the same process as in Example 4, it was not possible to obtain a crystal structure similar to that of Example 4. The impedance of the obtained sintered body was measured by the method described below, but the resistance of the sintered body could not be measured and the ionic conductivity could not be obtained as a numerical value.

[0228] Composition analysis was performed using the above method on the sintered bodies of ion-conductive solids containing oxides in Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342. The volume-average particle size of the ion-conductive solid powders and the ionic conductivity of the sintered bodies of ion-conductive solids obtained in Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342, and Comparative Examples 1 to 3, were measured using the following method. The methods for measuring ionic conductivity and volume-average particle size are described below. The obtained evaluation results are shown in Tables 1, 2, 3, and 4.

[0229] Measurement of Ionic Conductivity: Two large, parallel surfaces of the sintered plate-shaped ion-conductive solid containing oxide obtained by secondary firing were polished with sandpaper. The dimensions of the sintered plate-shaped ion-conductive solid containing oxide can be, for example, 0.9 cm x 0.9 cm x 0.05 cm, but are not limited to this. Polishing was performed by first polishing with #500 for 15 to 30 minutes, then with #1000 for 10 to 20 minutes, and finally with #2000 for 5 to 10 minutes. The polishing was completed when there were no visible irregularities or scratches on the polished surface. After polishing, a gold film was formed on the polished surface of the sintered plate of ion-conductive solid containing oxide using a Sanyu Electronics SC-701MkII ADVANCE sputtering system. The film formation conditions were Ar process gas, a vacuum level of 2 to 5 Pa, and a film formation time of 5 minutes. After film formation, the AC impedance of the measurement sample was measured. Impedance measurements were performed using an impedance / gain phase analyzer SI1260 and a dielectric interface system 1296 (both manufactured by Solartron), and the measurement conditions were a temperature of 27°C, an amplitude of 20 mV, and a frequency of 0.1 Hz to 1 MHz. The resistance of the sintered body of an ionically conductive solid containing an oxide was calculated using the Nyquist plot obtained from the impedance measurement and Scribner's AC analysis software ZVIEW. An equivalent circuit corresponding to the measurement sample was set in ZVIEW, and the resistance of the sintered body of an ionically conductive solid containing an oxide was calculated by fitting and analyzing the equivalent circuit and the Nyquist plot. The ionic conductivity was calculated from the calculated resistance, the thickness of the sintered body of an ionically conductive solid containing an oxide, and the electrode area using the following formula: Ionic conductivity (S / cm) = thickness of sintered body of ionically conductive solid containing an oxide (cm) / (resistance of sintered body of ionically conductive solid containing an oxide (Ω) × electrode area (cm ２ ))

[0230] The ionic conductivity (S / cm) of the sintered body of the ion-conductive solid is preferably, for example, 8.00×10 －９ More preferably, 1.00×10 －８ or more, and more preferably 1.00 × 10 －７ or more, and even more preferably 1.00 × 10 －６More preferably, it is 1.00×10 －５ The higher the conductivity, the better. There is no particular upper limit to the conductivity. For example, 1.00 × 10 －２ Below, 1.00 x 10 －３ Below, 1.00 x 10 －４ The following is the result.

[0231] Evaluation of volume average particle size The ion-conductive solid powder containing oxide obtained by ball milling (Fritsch Planetary Mill P-7) after primary firing was subjected to particle size distribution measurement using a Horiba Laser Diffraction / Scattering Particle Size Distribution Analyzer LA-960V2. The refractive index was set to 1.8, and ethanol was used as the measurement solvent. The concentration of the sample was adjusted so that the transmittance was 90 to 70%. The volume average particle size was calculated from the obtained frequency distribution.

[0232] Results Tables 1, 2, 3 and 4 show the stoichiometric amounts (general formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ The values ​​of a, b, c, and d in the table), volume average particle size, and ionic conductivity were summarized. As a result of the composition analysis, it was confirmed that the sintered bodies of ion-conductive solids containing oxides of Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342, and Comparative Examples 1 to 3 all had compositions in accordance with the stoichiometric amounts of the raw materials listed in Tables 1, 2, 3, and 4. Furthermore, the sintered bodies of ion-conductive solids containing oxides of Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342 were ion-conductive solids that exhibited high ionic conductivity even when fired at temperatures below 700°C.

[0233] In the table, Comparative Examples 1 to 3 have the general formula Li ６＋ａ－ｃ－２ｄ Y １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B３ O ９ It is an oxide represented by the formula:

[0234] In the table, Comparative Examples 1 to 3 have the general formula Li ６＋ａ－ｃ－２ｄ Y １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ It is an oxide represented by the formula:

[0235] In the table, Comparative Examples 1 to 3 have the general formula Li ６＋ａ－ｃ－２ｄ Y １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ It is an oxide represented by the formula:

[0236] In the table, Comparative Examples 1 to 3 have the general formula Li ６＋ａ－ｃ－２ｄ Y １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ It is an oxide represented by the formula:

[0237] Tables 1, 2, 3, and 4 show that the ionic conductivity of the ion-conductive solids produced in Examples 1, 101, 201, and 301 is improved compared to Comparative Example 1, and that higher ionic conductivity can be obtained by replacing Y with at least one element selected from the group consisting of Lu, Ho, Er, and Tm. It can be seen that higher ionic conductivity can be obtained by replacing Y in the compositions disclosed in the prior art with at least one element selected from the group consisting of Lu, Ho, Er, and Tm, which are metal elements with small ionic radii.

[0238] In Table 1, the ionic conductivity of the ion-conductive solids produced in Examples 1 to 3 was improved compared to Comparative Examples 1 to 3, and it was shown that higher ionic conductivity could be obtained by substituting Lu for Y. It can be seen that higher ionic conductivity can be obtained by substituting Lu, which has a smaller ionic radius, for Y in the composition disclosed in the prior art. Furthermore, the ionic conductivity of the ion-conductive solids produced in Examples 44 to 46 was improved compared to Examples 16, 26, and 32, respectively. Because the compositions and substitution elements differ from those disclosed in the prior art, differences in melting point, etc., may affect the density after firing, which may result in a different appropriate range for particle size.

[0239] In Table 2, the ionic conductivity of the ion-conductive solids produced in Examples 101 to 103 was improved compared to Comparative Examples 1 to 3, and it was shown that higher ionic conductivity could be obtained by substituting Ho for Y. It can be seen that higher ionic conductivity can be obtained by substituting Ho, which has a small ionic radius, for Y in the composition disclosed in the prior art. Furthermore, the ionic conductivity of the ion-conductive solids produced in Examples 142 to 144 was improved compared to Examples 115, 125, and 131, respectively. Because the compositions and substitution elements differ from those disclosed in the prior art, differences in melting point, etc., may affect the density after firing, which may result in a different appropriate range for particle size.

[0240] In Table 3, the ionic conductivity of the ion-conductive solids produced in Examples 201 to 203 was improved compared to Comparative Examples 1 to 3, indicating that higher ionic conductivity can be obtained by substituting Er for Y. It can be seen that higher ionic conductivity can be obtained by substituting Er, which has a smaller ionic radius, for Y in the composition disclosed in the prior art. Furthermore, the ionic conductivity of the ion-conductive solids produced in Examples 240 to 242 was improved compared to Examples 215, 225, and 231, respectively. Because the compositions and substitution elements differ from those disclosed in the prior art, differences in melting point, etc., can affect the density after firing, potentially resulting in a different optimum particle size range.

[0241] In Table 4, the ionic conductivity of the ion-conductive solids produced in Examples 301 to 303 was improved compared to Comparative Examples 1 to 3, indicating that higher ionic conductivity can be obtained by replacing Y with Tm. It can be seen that higher ionic conductivity can be obtained by replacing Y in the composition disclosed in the prior art with Tm, which has a smaller ionic radius. Furthermore, the ionic conductivity of the ion-conductive solids produced in Examples 340 to 342 was improved compared to Examples 315, 324, and 330, respectively. Because the compositions and substitution elements differ from those disclosed in the prior art, differences in melting point, etc., can affect the density after firing, potentially resulting in a different optimum particle size range.

Claims

1. General formula Li ６＋ａ－ｃ－２ｄ X １－ａ－ｂ－ｃ－ｄ M1 ａ M2 ｂ M3 ｃ M4 ｄ B ３ O ９ An ionically conductive solid comprising an oxide represented by the formula: (In the formula, X is at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm; M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba; M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc; M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti; M4 is at least one metal element selected from the group consisting of Nb and Ta; a is a real number satisfying 0.000≦a≦0.800, b is 0.000≦b≦0.900, c is 0.000≦c≦0.800, d is 0.000≦d≦0.800, and a, b, c, and d are real numbers satisfying 0.000≦a+b+c+d<1.

000. However, this does not include the case where X and M2 are the same metal element.)

2. 2. The ionically conductive solid according to claim 1, wherein 1-ab-cd satisfies 0.300≦1-ab-cd.

3. 2. The ionically conductive solid according to claim 1, wherein 1-ab-cd satisfies 0.500≦1-ab-cd.

4. 2. The ionically conductive solid according to claim 1, wherein a satisfies the condition 0.000≦a≦0.

400.

5. 2. The ionically conductive solid according to claim 1, wherein b satisfies 0.000≦b≦0.

500.

6. 2. The ionically conductive solid according to claim 1, wherein c satisfies the condition 0.000≦c≦0.

400.

7. 2. The ionically conductive solid according to claim 1, wherein d satisfies the condition 0.000≦d≦0.

400.

8. The ion-conducting powder according to claim 1, wherein the volume average particle size is 0.1 μm or more and 28.0 μm or less. solid.

9. A positive electrode and A negative electrode; An electrolyte; An all-solid-state battery having at least At least one selected from the group consisting of the positive electrode, the negative electrode, and the electrolyte comprises the ion-conducting solid according to any one of claims 1 to 8.

10. 10. The all-solid-state battery of claim 9, wherein at least the electrolyte comprises the ion-conducting solid.